US5580992A - Olefinic monomers containing pendant perfluorinated cyclic ether moieties - Google Patents
Olefinic monomers containing pendant perfluorinated cyclic ether moieties Download PDFInfo
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- US5580992A US5580992A US08/396,619 US39661995A US5580992A US 5580992 A US5580992 A US 5580992A US 39661995 A US39661995 A US 39661995A US 5580992 A US5580992 A US 5580992A
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- 239000000178 monomer Substances 0.000 title description 4
- 150000004292 cyclic ethers Chemical group 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 30
- 239000011737 fluorine Substances 0.000 claims abstract description 30
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 29
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 14
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 5
- 101100434171 Oryza sativa subsp. japonica ACR2.2 gene Proteins 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 abstract description 13
- 229920000642 polymer Polymers 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 101100386054 Saccharomyces cerevisiae (strain ATCC 204508 / S288c) CYS3 gene Proteins 0.000 abstract 1
- 101150035983 str1 gene Proteins 0.000 abstract 1
- 150000002576 ketones Chemical class 0.000 description 11
- -1 COF radical Chemical class 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000007701 flash-distillation Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 238000006459 hydrosilylation reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- 101100177155 Arabidopsis thaliana HAC1 gene Proteins 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 101100434170 Oryza sativa subsp. japonica ACR2.1 gene Proteins 0.000 description 1
- 101150108015 STR6 gene Proteins 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- HFEHLDPGIKPNKL-UHFFFAOYSA-N allyl iodide Chemical compound ICC=C HFEHLDPGIKPNKL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229920006136 organohydrogenpolysiloxane Polymers 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- ZSBJCQGJFPHZRC-UHFFFAOYSA-N prop-2-enyl 4-methylbenzenesulfonate Chemical compound CC1=CC=C(S(=O)(=O)OCC=C)C=C1 ZSBJCQGJFPHZRC-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000005424 tosyloxy group Chemical group S(=O)(=O)(C1=CC=C(C)C=C1)O* 0.000 description 1
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D321/00—Heterocyclic compounds containing rings having two oxygen atoms as the only ring hetero atoms, not provided for by groups C07D317/00 - C07D319/00
- C07D321/02—Seven-membered rings
- C07D321/04—Seven-membered rings not condensed with other rings
- C07D321/08—1,4-Dioxepines; Hydrogenated 1,4-dioxepines
Definitions
- the present invention relates to novel fluorine-containing compounds, and more particularly to fluorine-containing compounds having a perfluorocyclic ether group and a method of producing the same.
- fluorine-containing styrene derivatives compounds represented by the following general formula: ##STR3## wherein R 1 represents a hydrogen atom or a lower alkyl group, R 2 represents a hydrogen atom or a fluorine-containing group, R 3 represents a fluorine-containing group, X represents --O--or>Si (R) 2 in which R represents a lower alkyl group, Y represents a halogen atom, n is 0 or 1, and a is an integer of 0 to 4 are known (see Japanese Pre-examination Patent Publication (KOKAI) Nos. 62-104814 and 62-289538).
- the above fluorine-containing styrene derivatives can be homopolymerized or copolymerized with another polymerizable monomer to introduce a fluorine-containing group into various polymers and therefore very useful industrially.
- fluorine-containing groups (R 2 and R 3 ) in the above fluorine-containing styrene derivatives are a polyfluoroalkyl group or a perfluoroalkyl group having 1 to 10 carbon atoms and a branched fluorooxyalkyl group having an ether linkage represented by the following formula: ##STR4## That is, styrene derivatives having a perfluorocyclic ether group are not known at all.
- An object of the present invention is to provide novel and chemically quite stable fluorine-containing compounds having a perfluorocyclic ether group.
- a fluorine-containing compound represented by the following general formula (1): ##STR9## wherein A represents a group having the formula (2): ##STR10## wherein R represents a hydrogen atom or an alkyl group, or a group --CH 2 --CH ⁇ CH 2 .
- the present fluorine-containing compound having a perfluorocyclic ether group has a chemically stable structure and can be subjected to an addition reaction such as hydrosilylation, or homopolymerization or copolymerization with other olefinic monomers, using a free radical species, cation species or anion species as a polymerization initiator, to introduce the perfluorocyclic ether group into various compounds and polymers.
- a fluorine-containing compound having an allyl group is used, by hydrosilylation reaction, for example, with a silicon compound having an SiH group or SiH groups such as, e.g., organohydrogensilanes and organohydrogenpolysiloxanes, an organosilicon compound into which a perfluorocyclic ether group is introduced can be synthesized. Since such a perfluorocyclic ether group exhibits such properties as chemical resistance, water repellency, oil repellency, and weather resistance, the present invention is very useful to improve such properties.
- FIG. 1 is the IR chart of the present fluorine-containing compound obtained in Example 1.
- the present fluorine-containing compound includes, as its embodiments, a fluorine-containing compound represented by the following general formula (3): ##STR11## wherein R has the same meaning as defined for the formula (2), and a fluorine-containing compound represented by the formula (4 ): ##STR12##
- the alkyl group represented by R in the above general formulas (2) and (3) includes an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like.
- a preferable alkyl group is a lower alkyl group having 3 or less carbon atoms.
- Particularly preferred R in the formula (2) or (3) are a hydrogen atom and the methyl group in view of availability of raw materials or stability of products.
- the compounds have a styrene structure or an allyl group in the molecule, they can be homopolymerized or copolymerized with other polymerizable monomer and are useful as a raw material for the production of a polymer having perfluorocyclic ether groups in the side chains or as pendant groups.
- the perfluorocyclic ketone represented by the above formula (5) is a known compound, is described, for example, in U.S. Pat. No. 5,247,101 and Japanese Pre-examination Patent Publication (KOKAI) No. 4-316576, and is synthesized in accordance with the method disclosed in the U.S. Patent or the Japanese Pre-examination Patent Publication.
- KKAI Japanese Pre-examination Patent Publication
- the eliminable group represented by Z in the above formula (6) includes, for example, a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, and a tosyloxy group.
- the compound represented by the above formula (6) is used generally in an amount of 0.3 to 1.5, preferably 1 to 1.5 moles per mole of the above perfluorocyclic ketone.
- an alkali fluoride such as sodium fluoride, potassium fluoride, and cesium fluoride
- a quaternary ammonium salt such as tetrabutylammonium fluoride
- the fluoride anion source is preferably used in an amount of 1 to 1.5 moles per mole of the above perfluorocyclic ketone.
- any solvent can be used so long as it is inactive for the reaction, and generally an aprotic polar solvent, such as glyme, diglyme, triglyme, tetraglyme, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and acetonitrile, is preferable.
- the amount of the solvent to be preferably used is 0.1 to 20 liters, preferably 0.5 to 20 liters per mole of the above perfluorocyclic ketone.
- the reaction To carry out the reaction, out of the above raw material components, particularly the fluoride anion source and the solvent are previously dehydrated and then are used, which is desirable to allow the reaction to proceed smoothly.
- the reaction is carried out in such a way that these raw materials are mixed under nonaqueous conditions and are allowed to react at a temperature of 0 to 200° C., and preferably 30 to 150° C., for about 1 hour to 10 days with stirring.
- the obtained compound of the present invention can be isolated by means of distillation or the like.
- the fluorine-containing compound represented by the above general formula (3) can be produced, for example, by causing a perfluorocyclic ketone represented by the above formula (5) to react with a styrene compound represented by the above formula (7) in the presence of the above fluoride anion source and the above solvent.
- the compound represented by the above formula (4) can be produced, for example, by causing a perfluorocyclic ketone represented by the above formula (5) to react with the allyl compound in the presence of the above fluoride anion source and the above solvent.
- the allyl compound is used preferably in an amount of 0.3 to 1.5 moles, more preferably 1.0 to 1.5 moles, per mole of the above perfluorocyclic ketone.
- the solvent is used in an amount of preferably 0.1 to 20 liters, more preferably 0.5 to 20 liters, per mole of the above perfluorocyclic ketone.
- reaction mixture thus obtained was subjected to flash distillation with the reaction mixture heated to 50 ° C. under a reduced pressure of 2 mmHg and thus 10.5 g of a fraction was obtained.
- GC analysis it was confirmed that the fraction contained the desired product in an amount of 72%.
- This fraction was distilled to isolate the product having a boiling point of 143° to 145 ° C. and various analyses of the fraction were carried out to confirm that the product was the compound represented by the above formula (4). The results of the analyses are shown below:
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A fluorine-containing compound represented by the following general formula (1): ##STR1## wherein A represents a group --CH2 --CH═CH2 or a group ##STR2## in which R represents a hydrogen atom or an alkyl group. The compound is useful as an intermediate for producing various compounds and can introduce perfluorocyclic ether groups into various polymers to give such properties as chemical resistance, water repellency, oil repellency, and weather resistance to the polymers.
Description
1. Field of the Invention
The present invention relates to novel fluorine-containing compounds, and more particularly to fluorine-containing compounds having a perfluorocyclic ether group and a method of producing the same.
2. Description of the Prior Art
Heretofore, as fluorine-containing styrene derivatives, compounds represented by the following general formula: ##STR3## wherein R1 represents a hydrogen atom or a lower alkyl group, R2 represents a hydrogen atom or a fluorine-containing group, R3 represents a fluorine-containing group, X represents --O--or>Si (R)2 in which R represents a lower alkyl group, Y represents a halogen atom, n is 0 or 1, and a is an integer of 0 to 4 are known (see Japanese Pre-examination Patent Publication (KOKAI) Nos. 62-104814 and 62-289538).
The above fluorine-containing styrene derivatives can be homopolymerized or copolymerized with another polymerizable monomer to introduce a fluorine-containing group into various polymers and therefore very useful industrially.
However, specifically indicated fluorine-containing groups (R2 and R3) in the above fluorine-containing styrene derivatives are a polyfluoroalkyl group or a perfluoroalkyl group having 1 to 10 carbon atoms and a branched fluorooxyalkyl group having an ether linkage represented by the following formula: ##STR4## That is, styrene derivatives having a perfluorocyclic ether group are not known at all.
Hitherto, as organic compounds having a perfluorocyclic ether group, compounds represented by the following formula: ##STR5## are known. Although these fluorine-containing organic compounds are used as an inactive liquid, the fluorine-containing compounds do not have a functional group and are poor in reactivity with other substances and therefore it cannot be expected to use the fluorine-containing compounds, for example, as a raw material for synthesis of other materials.
On the other hand, U.S. Pat. No. 4,033,984, U.S. Pat. No. 4,035,388, Japanese Patent Publication (KOKOKU) Nos. 59-42676, 60-15630, and 60-2291 disclose fluorine-containing compounds having a perfluorocyclic ether group and rich with reactivity derived from COF radical, represented by the following formula (i): ##STR6##
Further, perfluoro compounds represented by the following formulas (ii) and (iii): ##STR7## are reported (see GB Patent 1571356 A, Japanese Pre-examination Patent Publication (KOKAI) No. 53-82713).
Since all of these compounds represented by the formulas (i) to (iii) have a perfluorocyclic ether group and a reactivity, they are expected to be used as a raw material for synthesis of other compounds. However, as compounds having a perfluorocyclic ether group, compounds having an allyl group (--CH2 CH═CH2) or a group having an unsubstituted or lower alkyl-substituted stylyl group represented by the following general formula: ##STR8## wherein R stands for a hydrogen atom or a lower alkyl group, are not known.
An object of the present invention is to provide novel and chemically quite stable fluorine-containing compounds having a perfluorocyclic ether group.
According to the present invention there is provided a fluorine-containing compound represented by the following general formula (1): ##STR9## wherein A represents a group having the formula (2): ##STR10## wherein R represents a hydrogen atom or an alkyl group, or a group --CH2 --CH═CH2.
The present fluorine-containing compound having a perfluorocyclic ether group has a chemically stable structure and can be subjected to an addition reaction such as hydrosilylation, or homopolymerization or copolymerization with other olefinic monomers, using a free radical species, cation species or anion species as a polymerization initiator, to introduce the perfluorocyclic ether group into various compounds and polymers. In particular, if a fluorine-containing compound having an allyl group is used, by hydrosilylation reaction, for example, with a silicon compound having an SiH group or SiH groups such as, e.g., organohydrogensilanes and organohydrogenpolysiloxanes, an organosilicon compound into which a perfluorocyclic ether group is introduced can be synthesized. Since such a perfluorocyclic ether group exhibits such properties as chemical resistance, water repellency, oil repellency, and weather resistance, the present invention is very useful to improve such properties.
FIG. 1 is the IR chart of the present fluorine-containing compound obtained in Example 1.
The present fluorine-containing compound includes, as its embodiments, a fluorine-containing compound represented by the following general formula (3): ##STR11## wherein R has the same meaning as defined for the formula (2), and a fluorine-containing compound represented by the formula (4 ): ##STR12##
The alkyl group represented by R in the above general formulas (2) and (3) includes an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl and the like. A preferable alkyl group is a lower alkyl group having 3 or less carbon atoms. Particularly preferred R in the formula (2) or (3) are a hydrogen atom and the methyl group in view of availability of raw materials or stability of products.
Since the compounds have a styrene structure or an allyl group in the molecule, they can be homopolymerized or copolymerized with other polymerizable monomer and are useful as a raw material for the production of a polymer having perfluorocyclic ether groups in the side chains or as pendant groups.
The fluorine-containing compound represented by the above general formula (1) can be produced, for example, by causing a perfluorocyclic ketone represented by the following formula (5): ##STR13## to react with a compound represented by the following formula (6):
A-Z (6)
wherein A has the same meaning as defined above and Z represents an eliminable group, in the presence of a fluoride anion source and a solvent.
The perfluorocyclic ketone represented by the above formula (5) is a known compound, is described, for example, in U.S. Pat. No. 5,247,101 and Japanese Pre-examination Patent Publication (KOKAI) No. 4-316576, and is synthesized in accordance with the method disclosed in the U.S. Patent or the Japanese Pre-examination Patent Publication.
The compound of the formula (6) includes, for example, a substituted or unsubstituted styrene compound having the general formula (7): ##STR14## wherein R is as defined for the formula (2) and Z is as defined above, and an allyl compound of the formula:
CH.sub.2 ═CH--CH.sub.2 13 Z
wherein Z is as defined above.
The eliminable group represented by Z in the above formula (6) includes, for example, a halogen atom such as a chlorine atom, a bromine atom and an iodine atom, and a tosyloxy group.
The allyl compound includes, for example, allyl chloride, allyl bromide, allyl iodide, and allyl p-toluenesulfonate.
Preferably, the compound represented by the above formula (6) is used generally in an amount of 0.3 to 1.5, preferably 1 to 1.5 moles per mole of the above perfluorocyclic ketone.
As the fluoride anion source, for example, an alkali fluoride, such as sodium fluoride, potassium fluoride, and cesium fluoride, and a quaternary ammonium salt, such as tetrabutylammonium fluoride, are preferably used. The fluoride anion source is preferably used in an amount of 1 to 1.5 moles per mole of the above perfluorocyclic ketone.
As the solvent, any solvent can be used so long as it is inactive for the reaction, and generally an aprotic polar solvent, such as glyme, diglyme, triglyme, tetraglyme, diethyl ether, tetrahydrofuran, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, and acetonitrile, is preferable. The amount of the solvent to be preferably used is 0.1 to 20 liters, preferably 0.5 to 20 liters per mole of the above perfluorocyclic ketone.
To carry out the reaction, out of the above raw material components, particularly the fluoride anion source and the solvent are previously dehydrated and then are used, which is desirable to allow the reaction to proceed smoothly. The reaction is carried out in such a way that these raw materials are mixed under nonaqueous conditions and are allowed to react at a temperature of 0 to 200° C., and preferably 30 to 150° C., for about 1 hour to 10 days with stirring. After the completion of the reaction, the obtained compound of the present invention can be isolated by means of distillation or the like.
The fluorine-containing compound represented by the above general formula (3) can be produced, for example, by causing a perfluorocyclic ketone represented by the above formula (5) to react with a styrene compound represented by the above formula (7) in the presence of the above fluoride anion source and the above solvent.
The compound represented by the above formula (4) can be produced, for example, by causing a perfluorocyclic ketone represented by the above formula (5) to react with the allyl compound in the presence of the above fluoride anion source and the above solvent.
Generally, the allyl compound is used preferably in an amount of 0.3 to 1.5 moles, more preferably 1.0 to 1.5 moles, per mole of the above perfluorocyclic ketone.
The solvent is used in an amount of preferably 0.1 to 20 liters, more preferably 0.5 to 20 liters, per mole of the above perfluorocyclic ketone.
After 82.2 g (0.54 mole) of dehydrated cesium fluoride, 241 g of dehydrated tetraglyme, and 166.6 g (0.46 mole) of a perfluorocyclic ketone represented by the above formula (5) were charged into a 1-liter glass reactor, they were stirred under a nitrogen atmosphere at room temperature for 2 hours. Then 34.0 g (0.22 mole) of p-chloromethylstyrene and 20 mg of p-methoxyphenol (polymerization inhibitor) were added, and they were stirred under a nitrogen atmosphere at 95° C. for 11 hours.
The resulting reaction mixture was subjected to flash distillation under reduced pressure to obtain 210.9 g of a fraction. By GC analysis, it was confirmed that the fraction contained 6.1% of a desired product. The fraction was further distilled to isolate a product having a boiling point of 85° to 86° C. and the product was subjected to various analyses. As a result, it was confirmed that the product was a styrene derivative represented by the following formula (1a): ##STR15##
The results of the analyses are shown below:
19 F-NMR: (CCl4 solution, CF3 COOH standard)
-57.5 to-51.9 ppm (m, 3F; >CF-)
-9.0 to-2.3 ppm (m, 10F; --CF3, --CF2 O--)
1 H-NMR: (CCl4 solution, TMS standard)
4.4 ppm (s, 2H; --CH2 O--)
5.2 ppm (dd, 1H; ##STR16## 5.6 ppm (dd, 1H; ##STR17## 6.6 ppm (dd, 1H; ##STR18## 7.2 ppm (m, 4H; ##STR19## GC-MS: M+ =496, 117 ##STR20## 100 (C2 F4), 69 (CF3) IR: shown in FIG. 1.
18.0 g (50 mmol) of a perfluorocyclic ketone represented by the above formula (5), 9.9 g (65 mmol) of dehydrated cesium fluoride, 30 ml of dehydrated tetraglyme, and 6.0 g (50 mmol) of allyl bromide were charged into a 100-ml of glass reactor and they were stirred under a nitrogen atmosphere at 70 ° C. for 4 hours.
Then, the reaction mixture thus obtained was subjected to flash distillation with the reaction mixture heated to 50 ° C. under a reduced pressure of 2 mmHg and thus 10.5 g of a fraction was obtained. By GC analysis, it was confirmed that the fraction contained the desired product in an amount of 72%.
This fraction was distilled to isolate the product having a boiling point of 143° to 145 ° C. and various analyses of the fraction were carried out to confirm that the product was the compound represented by the above formula (4). The results of the analyses are shown below:
1 H-NMR: (CCl4 solution, TMS standard)
4.4 ppm (m, 2H; --CH2 --)
5.1 to 5.4 ppm (m, 2H; CH2 ═)
5.6 to 6.2 ppm (m, 1H; ═CH--)
19 F-NMR: (CCl4 solution, CF3 COOH standard)
-57.4 to-52.8 ppm (m, 3F; >CF--)
-9.4 to-2.6 ppm (m, 10F; --CF2 O--, --CF3)
IR:
1650 cm-1 (CH2 ═CH--)
GC-MS:
M+ =420, 69 (CF3), 41 (C3 H5)
Claims (6)
1. A fluorine-containing compound represented by the following general formula (1): ##STR21## wherein A represents a group --CH2 --CH═CH2 or a group ##STR22## in which R represents a hydrogen atom or an alkyl group.
2. The fluorine-containing compound of claim 1, represented by the following general formula (3): ##STR23## wherein R represents a hydrogen atom or an alkyl group.
3. The fluorine-containing compound of claim 1, represented by the following formula (4): ##STR24##
4. The fluorine-containing compound of claim 2, wherein R represents a hydrogen atom.
5. The fluorine-containing compound of claim 2, wherein R represents an alkyl group having 1 to 4 carbon atoms.
6. The fluorine-containing compound of claim 5, wherein said alkyl group is a lower alkyl group having 3 or less carbon atoms.
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| JP6-055279 | 1994-03-01 | ||
| JP5527994 | 1994-03-01 | ||
| JP6-055280 | 1994-03-01 | ||
| JP5528094 | 1994-03-01 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001028998A1 (en) * | 1999-10-21 | 2001-04-26 | Ciba Specialty Chemicals Holding Inc. | N-substituted perfluoroalkylated pyrrolidines, process for making them and process for the addition of rf-iodide to an olefin |
| US20060135673A1 (en) * | 2004-12-15 | 2006-06-22 | Temperante John A | Fluorochemical esters blends as repellent polymer melt additives |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3382222A (en) * | 1965-02-18 | 1968-05-07 | Agriculture Usa | Fluorinated allyl ethers and use thereof |
| US4793352A (en) * | 1986-02-07 | 1988-12-27 | Eichenlaub John E | Limited heat transfer device and method |
| US5254699A (en) * | 1991-04-16 | 1993-10-19 | Shin-Etsu Chemical Co., Ltd. | Cyclic perfluoroethers and method of making |
-
1995
- 1995-03-01 US US08/396,619 patent/US5580992A/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3382222A (en) * | 1965-02-18 | 1968-05-07 | Agriculture Usa | Fluorinated allyl ethers and use thereof |
| US4793352A (en) * | 1986-02-07 | 1988-12-27 | Eichenlaub John E | Limited heat transfer device and method |
| US5254699A (en) * | 1991-04-16 | 1993-10-19 | Shin-Etsu Chemical Co., Ltd. | Cyclic perfluoroethers and method of making |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001028998A1 (en) * | 1999-10-21 | 2001-04-26 | Ciba Specialty Chemicals Holding Inc. | N-substituted perfluoroalkylated pyrrolidines, process for making them and process for the addition of rf-iodide to an olefin |
| US6436235B1 (en) | 1999-10-21 | 2002-08-20 | Ciba Specialty Chemicals Corporation | N-substituted perfluoroalkylated pyrrolidines and process for making them |
| US20060135673A1 (en) * | 2004-12-15 | 2006-06-22 | Temperante John A | Fluorochemical esters blends as repellent polymer melt additives |
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